Method for producing fluorinated organic compounds

ABSTRACT

Provided is a process for making 2-chloro-1,1,1,2-tetrafluoropropane. The process has the step of hydrofluorinating 2-chloro-3,3,3-trifluoropropene in the presence of a catalyst selected from the group consisting of SbCl 3 , SbCl 5 , SbF 5 , TiCl 4 , SnCl 4 , Cr 2 O 3 , and fluorinated Cr 2 O 3 .

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a Continuation of U.S. application Ser. No.14/704,491, filed May 5, 2015, which application is a Continuation ofU.S. application Ser. No. 12/631,728, filed Dec. 4, 2009, (now U.S. Pat.No. 9,024,092, issued May 5, 2015), which application is aContinuation-In-Part (CIP) of U.S. application Ser. No. 11/619,592,filed Jan. 3, 2007, (now U.S. Pat. No. 8,084,653, issued Dec. 27, 2011),which in turn, claims the priority benefit of U.S. ProvisionalApplication No. 60/755,485, filed Jan. 3, 2006. application Ser. No.12/631,728 is also a continuation of U.S. application Ser. No.12/338,466, filed Dec. 18, 2008 (abandoned), which in turn claims thepriority benefit of U.S. Provisional Application No. 61/021,121, filedJan. 15, 2008. Each of these applications are incorporated herein byreference.

BACKGROUND OF THE INVENTION 1. Field of the Invention

The present invention relates to a process for making2-chloro-1,1,1,2-tetrafluoropropane. The present invention furtherrelates to a process for making 2-chloro-1,1,1,2-tetrafluoropropane viahydrofluorination of 2-chloro-3,3,3-trifluoropropene with highsingle-pass conversion.

2. Description of the Related Art

The refrigerant and blowing agent 2,3,3,3-tetrafluoropropene (1234yf) isproduced from the dehydrochlorination of2-chloro-1,1,1,2-tetrafluoropropane (244bb). 244bb may be manufacturedfrom 2-chloro-3,3,3-trifluoropropene (1233xf).

When conversion of 2-chloro-1,1,1,2-tetrafluoropropane from2-chloro-3,3,3-trifluoropropene is low,2-chloro-1,1,1,2-tetrafluoropropane and 2-chloro-3,3,3-trifluoropropeneare present in admixture in product streams.2-chloro-1,1,1,2-tetrafluoropropane and 2-chloro-3,3,3-trifluoropropeneexhibit similar boiling points and azeotrope-like properties that makethem difficult to separate via standard techniques such as conventionaldistillation.

One method of addressing the problem of low conversion is to increaserecycle of product streams to the reactor so that additional conversionis obtained. The increased recycle would require process equipment to beincreased in size and scale to maintain a desired level or productoutput, and, thus significantly increase manufacturing cost. Inaddition, the separation of components in the product stream isdifficult.

It would be desirable to have a process for making2-chloro-1,1,1,2-tetrafluoropropane from 2-chloro-3,3,3-trifluoropropeneat higher single-pass conversion levels.

SUMMARY OF THE INVENTION

Provided is a process for making 2-chloro-1,1,1,2-tetrafluoropropane.The process has the step of hydrofluorinating2-chloro-3,3,3-trifluoropropene in the presence of a catalyst selectedfrom the group consisting of SbCl₃, SbCl₅, SbF₅, TiCl₄, SnCl₄, Cr₂O₃,and fluorinated Cr₂O₃. Preferably, the process is performed as acontinuous process.

DETAILED DESCRIPTION OF THE INVENTION

In the process of the present invention, selected catalysts are employedto enhance the single-pass conversion of 2-chloro-3,3,3-trifluoropropeneto 2-chloro-1,1,1,2-tetrafluoropropane via HF addition across the doublebond of 2-chloro-3,3,3-trifluoropropene. The catalysts are thefollowing: SbCl₃, SbCl₅, SbF₅, TiCl₄, SnCl₄, Cr₂O₃, and fluorinatedCr₂O₃.

The catalyst may be supported or in bulk form (unsupported). Usefulcatalyst supports include carbon, alumina, fluorinated alumina, aluminumfluoride, alkaline earth metal oxides, fluorinated alkaline earthmetals, zinc oxide, zinc fluoride, tin oxide, and tin fluoride.

The catalyst optionally may be activated prior to and during use. Usefulactivating agents include anhydrous hydrogen fluoride and chlorine. Thecatalyst is kept activated by the continuous or batch addition of anoxidizing agent such as Cl₂.

The hydrofluorination process may be carried out in a vapor phase or aliquid phase.

In vapor-phase hydrofluorination, HF (hydrogen fluoride gas) is fedcontinuously through the catalyst bed. After a short time with only theHF feed stream, 2-chloro-3,3,3-trifluoropropene is fed continuouslythrough the catalyst bed at a ratio of about 1:1 to about 1:30 andpreferably from about 1:2 to about 1:15(2-chloro-3,3,3-trifluoropropene/HF mole ratio). The reaction between HFand 2-chloro-3,3,3-trifluoropropene is carried out at a temperature fromabout 30° C. to about 200° C. (preferably from about 50° C. to about120° C.) and at a pressure of about 5 psia to about 200 psia (pounds persquare inch absolute) (preferably from about 30 psia to about 175 psia).The catalyst may be supported on a substrate, such as on activatedcarbon, or may be unsupported or free-standing. The catalyst may (or maynot) have to be activated with anhydrous hydrogen fluoride HF (hydrogenfluoride gas) and/or Cl₂ (chlorine gas) before use depending on thestate of the catalyst. If necessary, the catalyst can be kept activatedby the continuous or batch addition of Cl₂ or a similar oxidizing agent.

In liquid phase hydrofluorination, the catalyst is charged in a liquidform to a reactor and optionally activated with HF. The activatedcatalyst is then heated to the desired reaction temperature of about 30°C. to about 200° C. (preferably from about 50° C. to about 120° C.) andthe pressure is kept between about 15 psia to about 200 psia (preferablyfrom about 50 psia to about 175 psia). After a short time with only HFfeed, a 2-chloro-3,3,3-trifluoropropene feed stream is fed continuouslythrough the catalyst bed at a ratio of about 1:1 to about 1:30 andpreferably about 1:2 to about 1:15 (2-chloro-3,3,3-trifluoropropene/HFmole ratio). If necessary, the catalyst can be kept activated by thecontinuous or batch addition of Cl₂ or a similar oxidizing agent.

Enhanced or improved single-pass conversion of2-chloro-3,3,3-trifluoropropene to 2-chloro-1,1,1,2-tetrafluoropropaneis an important feature of the present invention. The hydrofluorinationreaction is preferably carried out to attain a conversion of about 70%or more, preferably about 90% or more, and most preferably about 93% ormore. Conversion is calculated by the number of moles of reactant(2-chloro-3,3,3-trifluoropropene) consumed divided by number of moles ofreactant (2-chloro-3,3,3-trifluoropropene) fed to the reactor multipliedby 100. The selectivity for 2-chloro-1,1,1,2-tetrafluoropropane attainedis preferably about 60% or more and most preferably about 80% or more.Selectivity is calculated by number of moles of product(2-chloro-1,1,1,2-tetrafluoropropane) formed divided by number of molesof reactant consumed.

Hydrofluorination is preferably carried out in a corrosion-resistantreaction vessel. Examples of corrosion-resistant materials areHastelloy, Nickel, Incoloy, Inconel, Monel and fluoropolymer linings.The vessel may have a fixed or a fluidized catalyst bed. If desired,inert gases such as nitrogen or argon may be employed in the reactorduring operation.

The following are examples of the present invention and are not to beconstrued as limiting. Unless otherwise indicated, all percentages andparts are by weight.

EXAMPLES Example 1

The vapor phase fluorination of the 2-chloro-3,3,3-trifluoropropene(1233xf)+HF→2-chloro-1,1,1,2-tetrafluoropropane (244bb) was carried out.The fluorination catalyst for the experiment was 50 wt % SbCl₅impregnated on 50 wt % Calgon PCB activated carbon.

Several kilograms of 50 weight % SbCl₅ on activated carbon were producedin the lab. The catalyst was first passed through a 10-mesh sieve toremove fines. A total of 2272.6 grams (or about 2800 cc) was charged totwo 2-inch vapor-phase pipe reactors in series and installed in a sandbath for controlled heating.

The catalyst was activated by adding a minimum of a 5:1 mole ratio of HFto SbCl₅, followed by a Cl₂ addition of a minimum of a 3:1 mole ratio ofCl₂ to SbCl₅. Finally, a large excess of HF was passed through thecatalyst bed for 2 hours.

The reaction was run using 2-chloro-3,3,3-trifluoropropene crude rawmaterial with various compositions as organic feed to produce2-chloro-1,1,1,2-tetrafluoropropane. The reactor effluent was collectedin a distillation column before removal of excess HF. During theexperiment, a 93.5% conversion of 2-chloro-3,3,3-trifluoropropene wasachieved. The maximum selectivity of 2-chloro-1,1,1,2-tetrafluoropropaneachieved was 98.4% on a molar basis. The reaction ran continuously for76.5 hrs without attempting catalyst regeneration with Cl₂. The catalystbegan showing signs of deactivation after about 65 hours on-stream time.The experimental data and reaction conditions are shown below in Tables1A to 1D.

TABLE 1A On-stream 1233xf 1233xf HF feed Contact time T P feed rate feedrate HF feed rate rate mole ratio Catalyst Time (hrs) (° C.) (Mpa)Catalyst (mmole/min) (g/hr) (mmole/min) (g/hr) HF:1233xf (ml) (sec) 1-23 72 0.33 SbCl₅/C 12.0 95.3 185.2 222.3 15.5 2800 99 23-29 72 0.33SbCl₅/C 18.3 145.2 215.5 258.6 11.8 2800 84 29-42 72 0.33 SbCl₅/C 23.4186.0 241.9 290.3 10.3 2800 74 42-53 74 0.33 SbCl₅/C 30.2 240.4 275.9331.1 9.1 2800 64 53-60 76 0.33 SbCl₅/C 39.3 322.1 317.5 381.0 8.1 280054   60-65.5 77 0.33 SbCl₅/C 48.1 394.6 400.7 480.8 8.3 2800 4365.5-73.5 80 0.33 SbCl₅/C 51.1 408.2 404.5 485.4 7.9 2800 42 73.5-76.579 0.33 SbCl₅/C 33.9 281.2 355.3 426.4 10.5 2800 49

TABLE 1B Feed composition (GC area %) On-stream 1234yf/ Time (hrs) 245cb244bb 1233xf 1232xf 1223xd others  1-23 0 0.31 82.41 17.03 0 0.25 23-290 0.31 82.41 17.03 0 0.25 29-42 0 0.31 82.41 17.03 0 0.25 42-53 0 0.3182.41 17.03 0 0.25 53-60 trace 31.08 68.92 0 0 0   60-65.5 trace 31.0868.92 0 0 0 65.5-73.5 0.69 21.41 77.36 0 trace 0.54 73.5-76.5 0.03 38.8661.09 0 0 0.02

TABLE 1C Reactor Effluent Composition (GC area %) On-stream 1234yf/ Time(hrs) 245cb 244bb 1233xf 1232xf 1223xd others  1-23 3.0 86.2 7.5 0.2 0.13.0 23-29 1.3 91.7 5.1 0.2 0.1 1.7 29-42 0.9 92.1 4.8 0.2 0.0 1.9 42-530.9 91.3 5.9 0.1 0.0 1.8 53-60 0.6 92.0 7.1 0.0 0.0 0.4   60-65.5 0.790.0 8.9 0.0 0.0 0.5 65.5-73.5 1.6 87.1 10.2 0.0 trace 1.1 73.5-76.5 1.486.3 11.6 0.0 0.0 0.8

TABLE 1D Selectivities (molar basis presuming (GC area % = wt %) 1233xf1232xf 1234yf/ Conversion Conversion 245cb 244bb 1232xf 1223xd others89.9 99.0 3.9 92.6 NA 0.1 3.2 93.2 98.8 1.6 96.4 NA 0.0 1.8 93.5 99.01.2 96.6 NA 0.0 2.0 92.0 99.3 1.1 96.9 NA 0.0 1.9 83.8 NA 1.0 98.4 0.00.0 0.6 82.8 NA 1.2 98.1 0.0 0.0 0.7 81.5 NA 1.5 97.8 0.0 0.0 0.7 75.1NA 3.1 95.5 0.1 0.0 1.6

Example 2

The liquid phase fluorination reaction of2-chloro-3,3,3-trifluoropropene(1233xf)+HF→2-chloro-1,1,1,2-tetrafluoropropane (244bb) was carried out.The fluorination catalyst for the experiment was SbCl₅.

About 6100 grams of SbCl₅ were contained in a Teflon™-lined liquid phasereactor (Teflon is a trademark of E.I. duPont de Nemours & Co) equippedwith a 2-inch ID (inside diameter) packed column and a condenser. Thereactor was 2.75-inch ID×36-inch L (length). Initially, a greater than5:1 mole ratio of HF was added to the reactor to fluorinate thecatalyst. A greater than 3:1 mole ratio of Cl₂ was then added to thereactor to ensure that the catalyst was brought back to a pentavalentstate. The reactor was heated to about 85° C.-87° C. HF feed was startedfirst. When an additional 1.3 lbs of HF had been added the2-chloro-3,3,3-trifluoropropene feed was started. The purity of the2-chloro-3,3,3-trifluoropropene feed stock was about 98 GC area % (gaschromatograph). The experiment ran continuously for 71 hours. For thisrun, chlorine was fed batchwise about every 4 hours throughout the runto keep the catalyst active. The HF and 2-chloro-3,3,3-trifluoropropenefeeds were varied during the run. The feeds averaged 0.495 lbs/hr HF,and 0.408 lbs/hr 2-chloro-3,3,3-trifluoropropene (chlorine was 5.4% byweight of organic) for a 7.9/1 ratio ofHF/2-chloro-3,3,3-trifluoropropene, and 135 seconds residence time atthe beginning of the run. In the middle of the run, the feeds averaged0.843 lbs/hr HF (pounds/hour) and 0.66 lbs/hr2-chloro-3,3,3-trifluoropropene (chlorine was 3.3% by weight of organic)for a 8.33/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 80 secondsresidence time. For the end of the run, the rate was increased. Thefeeds for this period averaged 1.42 lbs/hr HF and 1.24 lbs/hr2-chloro-3,3,3-trifluoropropene (chlorine was 2% by weight of organic)for a 7.5/1 ratio of HF/2-chloro-3,3,3-trifluoropropene, and 47 secondsresidence time. The level of unreacted 2-chloro-3,3,3-trifluoropropeneappeared to increase late in the run, which could have been the resultof lower Cl₂ level or shorter residence time.

The reactor temperature range for the experiment was 78-91° C. and thepressure range was 85 psig-115 psig (pounds per square inch gauge).

The following Table 2 contains the 2-chloro-3,3,3-trifluoropropeneconversion and product selectivity data:

TABLE 2 (Conversion and Selectivity on a Molar Basis) elapsed timeHFC245cb HCFC244bb HCFC1233xf HCFC235da HCFC1223xd Others Temp (Hours)Selectivity Selectivity Conversion Selectivity Selectivity Selectivity °C. 2 64.8 24.2 99.3 0.0 0.0 11.1 87.1 3 68.2 24.2 99.2 0.9 4.8 1.9 90.54 67.5 24.3 99.8 0.6 3.6 3.9 90.2 5 64.6 30.0 99.9 1.2 3.1 1.1 90.4 667.4 27.2 99.8 1.2 3.1 1.0 85.7 8 82.8 15.6 99.7 0.4 0.8 0.5 78.9 9 78.520.2 99.9 0.3 0.6 0.4 78.9 10 65.4 32.3 99.6 0.6 1.0 0.6 83.2 11 61.835.8 99.0 0.6 1.0 0.7 78.5 12 64.8 33.7 99.3 0.5 0.6 0.4 79.6 13.5 61.637.0 99.8 0.5 0.5 0.4 80.9 14 62.1 36.5 99.7 0.5 0.5 0.5 81.3 15 61.936.8 99.6 0.5 0.4 0.4 78.9 16 29.1 68.3 99.5 1.3 0.6 0.7 86.9 17 30.567.3 98.6 1.2 0.5 0.5 88.5 18 24.4 73.0 98.8 1.5 0.6 0.5 84.5 19 31.066.1 98.3 1.6 0.7 0.5 87.5 20 28.7 66.8 99.8 2.5 1.2 0.9 84.5 21 33.862.9 99.7 1.8 0.9 0.6 86.9 22 51.6 46.6 99.5 0.9 0.5 0.5 86.6 23 54.345.1 99.7 0.2 0.1 0.2 85.6 24 28.3 70.1 99.5 0.8 0.4 0.4 86.9 25 23.074.8 99.0 1.1 0.6 0.5 86.4 26 16.0 76.2 98.3 3.6 2.8 1.3 86.3 27 20.873.2 98.3 2.7 2.1 1.2 85.5 28 12.0 78.3 99.0 3.2 2.7 3.8 87 29 11.9 79.898.7 2.1 2.0 4.2 87.9 30 11.0 80.8 98.6 2.1 2.0 4.2 87.1 31 13.9 81.798.2 0.8 1.0 2.6 86.2 32 10.2 86.6 99.3 0.4 0.7 2.2 85.9 33 9.4 87.998.8 0.2 1.4 1.0 85.5 34 12.6 85.8 98.5 0.1 0.7 0.8 85.4 35 15.1 83.698.1 0.1 0.5 0.7 85.3 36 4.3 92.3 98.2 0.1 2.2 1.1 85.2 37 4.7 92.3 97.90.1 1.8 1.2 84.9 38 4.8 92.7 97.9 0.1 1.5 1.0 85.4 39.5 8.6 89.5 97.80.0 0.1 1.8 85.1 41.7 17.1 81.4 98.1 0.0 0.6 0.9 85 42.7 14.0 85.7 97.80.0 0.1 0.3 83.6 44.7 20.4 79.1 98.1 0.0 0.0 0.4 80.6 46 6.0 92.5 98.30.0 0.9 0.5 84.2 47.5 6.1 91.1 99.7 0.0 1.5 1.3 86.2 48 6.2 91.5 99.90.0 1.3 1.0 87.1 49 10.6 86.8 98.9 0.0 1.7 0.9 86.9 50 7.2 91.0 98.1 0.01.1 0.7 86.6 51 10.9 88.4 97.7 0.0 0.3 0.4 86.7 52 13.9 82.9 98.7 0.02.3 0.9 89.3 53 12.7 86.0 97.9 0.0 0.6 0.8 87.5 54 9.5 89.4 97.7 0.0 0.50.6 88 55 6.6 92.2 98.3 0.0 0.6 0.7 87.1 56 6.8 89.6 98.1 0.0 2.7 1.087.4 57 7.5 91.1 97.6 0.0 0.7 0.7 87.7 58.1 5.4 91.6 99.8 0.1 1.4 1.687.6 60 6.2 92.7 98.8 0.0 0.2 0.9 87.8 65.3 0.0 99.4 96.9 0.0 0.2 0.3 8866 5.2 91.7 99.7 0.1 2.0 1.0 87.2 69 3.3 96.2 96.1 0.1 0.2 0.3 88 70 3.095.1 95.3 0.1 1.3 0.5 87.9 71 2.8 95.4 96.8 0.0 0.4 1.4 88.5

Example 3

Example 3 used the same equipment as Example 2.

About 5615 grams of SbCl₅ were contained in the same reactor as that ofExample 2. The reactor was heated to about 85° C.-87° C. HF feed wasstarted first. After about 1.5 lbs of HF had been added, the2-chloro-3,3,3-trifluoropropene feed was started. The purity of the2-chloro-3,3,3-trifluoropropene feed stock was about 97.3 GC area %. Theexperiment ran continuously for 71 hours. For this run, Cl₂ was fedbatchwise about every 4 hours throughout the run to keep the catalystactive.

The Run # for this experiment was 36b. Conversion was immediately above98%, and remained that way throughout the rest of the run (throughFriday shut-down). The catalyst charge was left hot over the weekend,and operation resumed on Monday (now called Run #37), and similar highconversion was observed throughout the week. About 123 pounds ofacid-free 2-chloro-1,1,1,2-tetrafluoropropane crude was collectedbetween runs #36b and its continuation as Run #37 the following week.

The reactor temperature range for the experiment was 78° C.-86° C. andthe pressure range was 70 psig-105 psig. The organic crude materialcollected from the run was run on a gas chromatograph and exhibited thefollowing GC analysis.

The following Tables 3A and 3B set forth the2-chloro-3,3,3-trifluoropropene (1233xf) conversion and productselectivity data.

TABLE 3A (Run #36b, Conversion and Selectivity on a Molar Basis) ElapsedHF/Org molar molar molar molar molar molar Time Gas Temp moleselectivity selectivity conversion selectivity selectivity selectivity(Hours) Bag # (° C.) ratio HFC245cb HCFC244bb HCFC1233xf HCFC235daHCFC1232xf HCFC1223xd 35.3 1 84.1 0.64 0.26 98.69 0.01 0.02 0.06 35.336.3 2 85 0.43 0.54 98.70 0.01 0.00 0.01 36.3 37.3 3 85.2 0.55 0.4198.94 0.01 0.01 0.02 37.3 38.6 4 85.6 0.44 0.51 98.71 0.01 0.00 0.0238.6 39.2 5 83.6 0.30 0.63 97.77 0.01 0.01 0.03 39.2 39.7 6 85.5 0.250.70 97.26 0.01 0.01 0.02 39.7 40.8 7 86.9 0.36 0.59 98.08 0.01 0.000.03 40.8 41.6 8 83 0.55 0.44 98.94 0.00 0.00 0.01 41.6 42.4 9 85.9 0.400.58 98.40 0.00 0.00 0.01 42.4 43.4 10 85.3 0.37 0.61 98.42 0.00 0.000.00 43.4 44.75 11 83.1 0.29 0.70 98.37 0.00 0.01 0.01 44.75 45.5 12 800.23 0.76 98.44 0.00 0.00 0.00 45.5 46.5 13 81.7 0.21 0.76 98.40 0.000.00 0.01 46.5 47.5 14 81.3 0.19 0.79 98.21 0.00 0.00 0.01 47.5

TABLE 3B (Run #37, Conversion and Selectivity on a Molar Basis) ElapsedHF/Org molar molar molar molar molar molar Time Gas Temp moleselectivity selectivity conversion selectivity selectivity selectivity(Hours) Bag # (° C.) ratio HFC245cb HCFC244bb HCFC1233xf HCFC235daHCFC1232xf HCFC1223xd 1.3 1 87.5 11.84 0.16 0.82 98 0.002 0.002 0.0052.4 2 85.2 6.09 0.10 0.89 98 0.002 0.002 0.005 3.25 3 86.5 5.49 0.130.84 98 0.003 0.002 0.013 4.4 4 83.2 7.03 0.10 0.88 98 0.003 0.002 0.0175.4 5 83.3 8.80 0.10 0.88 98 0.002 0.001 0.008 6.4 6 81.5 8.00 0.08 0.9098 0.002 0.001 0.004 7.4 7 79.9 20.74 0.08 0.90 98 0.002 0.001 0.008 8.38 80 7.54 0.07 0.92 98 0.001 0.001 0.004 9.3 9 81.3 4.44 0.09 0.90 980.001 0.001 0.003 10.3 10 85.1 3.57 0.11 0.88 98 0.001 0.001 0.003 11.311 88 4.64 0.15 0.83 98 0.002 0.002 0.015 12.6 12 85.5 5.03 0.14 0.85 980.001 0.002 0.004 13.4 13 85.3 4.68 0.10 0.89 98 0.001 0.002 0.003 14.314 82.8 5.08 0.08 0.91 98 0.001 0.002 0.003 15.3 15 83.7 5.63 0.09 0.8998 0.002 0.001 0.012 16.25 16 84.2 7.21 0.08 0.91 98 0.001 0.001 0.00417.4 17 86.1 7.86 0.09 0.91 98 0.001 0.001 0.003 18.3 18 85.7 8.33 0.070.92 98 0.001 0.001 0.002 19.3 19 86 7.38 0.09 0.88 98 0.003 0.002 0.01820.3 20 87.8 8.27 0.09 0.90 98 0.002 0.001 0.003 21.4 21 83.4 10.48 0.080.88 98 0.002 0.003 0.003 22.4 22 88.7 18.21 0.08 0.91 98 0.001 0.0010.003 23.3 23 83 9.26 0.08 0.90 98 0.002 0.001 0.007 24.3 24 82.9 7.460.06 0.93 98 0.001 0.001 0.004 25.3 25 81.3 7.19 0.06 0.94 98 0.0010.001 0.003 26.3 26 83.9 8.05 0.05 0.94 98 0.001 0.001 0.003 27.3 2781.9 7.61 0.06 0.92 98 0.003 0.001 0.016 28.3 28 83.8 6.90 0.06 0.93 980.001 0.001 0.003 29.3 29 83.9 7.18 0.07 0.93 98 0.001 0.001 0.003 30.330 85 6.23 0.08 0.92 97 0.001 0.001 0.003 31.3 31 83.4 6.27 0.06 0.91 980.003 0.002 0.016 32.3 32 82.8 6.66 0.05 0.94 98 0.001 0.001 0.004 34.333 85.2 5.64 0.06 0.93 98 0.001 0.001 0.003 35.3 34 86 5.30 0.07 0.91 970.001 0.001 0.008 36.3 35 84.9 7.23 0.07 0.92 97 0.001 0.001 0.003 37.536 80.7 7.58 0.06 0.94 98 0.001 0.001 0.002 38.3 37 82.2 5.81 0.03 0.9798 0.001 0.002 0.003 39.25 38 81.9 6.32 0.04 0.94 98 0.002 0.002 0.01340.25 39 82 6.32 0.04 0.95 98 0.002 0.001 0.006 41.5 40 81.4 5.77 0.040.94 98 0.001 0.001 0.004 42.5 41 81 6.20 0.04 0.95 98 0.001 0.001 0.00343.8 42 81.4 8.14 0.03 0.96 98 0.001 0.001 0.003 44.7 43 80.7 8.14 0.030.97 98 0.000 0.001 0.001 45.5 44 80.9 6.88 0.03 0.97 98 0.000 0.0000.001 47 45 82.8 7.16 0.14 0.84 98 0.003 0.002 0.010 47.8 46 82.3 7.700.03 0.96 98 0.001 0.000 0.002 48.8 47 82.3 7.18 0.03 0.97 98 0.0000.000 0.001 49.8 48 82.5 6.67 0.03 0.97 98 0.000 0.000 0.001 50.8 4982.8 6.68 0.03 0.95 98 0.002 0.001 0.013 51.8 50 82.7 6.84 0.03 0.97 980.001 0.000 0.002 53 51 81.3 8.09 0.03 0.97 98 0.000 0.000 0.001 54.3 5279.8 8.60 0.03 0.97 98 0.000 0.000 0.001 54.8 53 81.2 4.22 0.03 0.95 980.002 0.001 0.015 56 54 81.6 6.75 0.03 0.97 98 0.000 0.000 0.002 56.8 5583.6 6.45 0.03 0.97 97 0.000 0.000 0.001 57.8 56 84.9 7.03 0.03 0.97 970.000 0.000 0.001 58.8 57 81.5 7.11 0.04 0.95 98 0.001 0.001 0.009 59.858 82.8 7.11 0.03 0.97 98 0.000 0.000 0.002 60.8 59 81.1 6.99 0.02 0.9898 0.000 0.000 0.001 63 60 84.2 7.51 0.02 0.96 98 0.001 0.001 0.010 6461 84 8.79 0.02 0.97 98 0.001 0.000 0.004 65 62 82.9 8.79 0.02 0.97 980.000 0.000 0.001 66 63 82.6 6.44 0.02 0.98 98 0.000 0.000 0.001 67 6483.2 7.33 0.03 0.94 98 0.005 0.001 0.015 68.25 65 82.1 5.28 0.04 0.95 980.002 0.001 0.004 69 66 83 7.22 0.03 0.96 98 0.001 0.000 0.002 70 6782.6 6.63 0.03 0.97 98 0.000 0.000 0.001 71 68 82.5 4.98 0.03 0.96 980.001 0.000 0.001 72 69 82.1 5.28 0.03 0.95 98 0.002 0.001 0.020 73 7081.1 4.75 0.02 0.97 98 0.000 0.001 0.002 74.25 71 82.2 4.77 0.03 0.97 980.000 0.000 0.001 75.1 72 87.1 5.20 0.03 0.97 98 0.000 0.000 0.001 75.873 81.3 4.09 0.03 0.95 98 0.001 0.001 0.016 78 74 81.4 8.64 0.02 0.97 980.000 0.000 0.002 79.1 75 80.4 7.16 0.02 0.98 98 0.000 0.000 0.001 80 7683.2 6.11 0.03 0.96 98 0.002 0.000 0.008 81.1 77 83.4 6.21 0.02 0.97 980.000 0.000 0.002 83.25 78 84 7.41 0.02 0.97 97 0.000 0.000 0.001 84.379 85.5 7.17 0.02 0.96 98 0.002 0.000 0.018 85 80 84.4 12.16 0.02 0.9898 0.001 0.000 0.003 86 81 82.1 9.15 0.02 0.98 98 0.000 0.000 0.001 8782 81.9 7.69 0.02 0.98 98 0.001 0.000 0.001 88.4 83 82.4 4.58 0.02 0.9498 0.007 0.001 0.031 89 84 83.4 9.46 0.02 0.97 98 0.001 0.000 0.004 9085 81.5 7.22 0.02 0.98 98 0.001 0.000 0.001 91.2 86 82.5 7.09 0.02 0.9898 0.000 0.000 0.001 92 87 83.4 7.49 0.01 0.97 98 0.001 0.001 0.015 9388 82.4 6.60 0.02 0.98 98 0.001 0.000 0.002 94 89 82.3 6.25 0.01 0.97 980.002 0.000 0.004 95 89.5 82.4 6.53 0.02 98 0.98 0.000 0.000 0.001 96.590 83.1 4.76 0.02 96 0.97 0.002 0.001 0.016 97 91 82.6 5.01 0.01 95 0.970.003 0.001 0.021 97.75 92 81 7.29 0.01 97 0.98 0.001 0.001 0.015 98.893 83.1 6.74 0.02 98 0.98 0.000 0.001 0.012 100.2 94 82.6 9.05 0.01 980.98 0.002 0.000 0.004 101.1 95 83.3 5.98 0.02 98 0.97 0.000 0.000 0.003102.3 96 85.5 5.11 0.02 97 0.97 0.000 0.000 0.001 103.1 97 82.7 5.220.02 97 0.97 0.001 0.001 0.007 104 98 82.4 5.11 0.02 97 0.98 0.000 0.0000.001 107 99 80.4 5.87 0.02 98 0.98 0.000 0.000 0.001 109 100 82.6 7.980.02 98 0.97 0.000 0.000 0.001 110 101 93.3 5.30 0.03 97 0.85 0.0000.001 0.001 111 102 88.8 4.86 0.03 85 0.82 0.000 0.001 0.001 112 10389.4 5.74 0.03 82 0.96 0.000 0.000 0.000 113 104 82.8 10.71 0.02 96 0.970.000 0.000 0.000 114 105 82.1 9.83 0.01 97 0.97 0.000 0.001 0.001

Example 4: Liquid-Phase Catalytic Fluorination of CF₃CCl═CH₂ (1233xf)with HF to CF₃CFClCH₃ (244bb)

About 327 grams of HF, about 50 grams 1233xf, and about 75 grams SbCl₅were charged into a 1-L autoclave. The reaction mixture was stirred at atemperature of about 80° C. for about 3 hours under about 620 psig ofpressure. After the reaction, the reactor was cooled to about 0° C. andabout 300 ml water was then added slowly into the autoclave over aperiod of about 45 min. After complete addition of water under stirring,the reactor was cooled to room temperature and then the overhead gaseswere transferred to another collecting cylinder. The yield of CF₃CFClCH₃was about 90% at a 1233xf conversion level of about 98%. The other majorby-products were CF₃CF₂CH₃ (2%), and an unidentified isomer of a C4compound of the general formula, C₄H₃Cl₃F₄ (8%).

Example 5: Liquid-Phase Catalytic Fluorination of CF₃CCl═CH₂ (1233xf)with HF to CF₃CFClCH₃ (244bb)

About 327 grams HF, about 50 grams 1233xf, and about 75 grams SbCl₅ werecharged into a 1-L autoclave. The reaction mixture was stirred at 80° C.for about 3 hours under about 625 psig of pressure. After the reaction,the reactor was cooled to about 45° C. and then the overhead gas mixturewas passed through a well dried KF, NaF, or Al₂O₃ (350 g) packed columnkept at about 80° C. to strip off HF from the gas stream. The gasescoming out of the column are collected in a cylinder kept in dry ice(−70° C.) bath. The yield of CF₃CFClCH₃ was 87% at a 1233xf conversionlevel of 93%. The other major by-products were CF₃CF₂CH₃ (1%), and anunidentified isomer of a C4 compound of the general formula, C₄H₃Cl₃F₄(7%). The product, CF₃CFClCH₃ was isolated by distillation with 98%purity.

Example 6: Gas-Phase Catalytic Fluorination of CF₃CCl═CH₂ (1233xf) withHF to CF₃CFClCH3 (244bb)

A 22-inch (½-inch diameter) Monel tube gas phase reactor was chargedwith about 120 cc of a catalyst. The reactor was mounted inside a heaterwith three zones (top, middle and bottom). The reactor temperature wasread by a custom made 5-point thermocouple kept at the middle inside ofthe reactor. The inlet of the reactor was connected to a pre-heater,which was kept at about 300° C. by electrical heating. Organic (1233xf)was fed from a cylinder kept at 70° C. through a regulator, needlevalve, and a gas mass-flow-meter. The organic line to the pre-heater washeat traced and kept at a constant temperature of about 73° C. byelectrical heating to avoid condensation. N₂ was used as a diluent insome cases and fed from a cylinder through a regulator and a mass flowcontroller into the pre-heater. All feed cylinders were mounted onscales to monitor their weight by difference. The reactions were run ata constant reactor pressure of from about 0 to about 100 psig bycontrolling the flow of reactor exit gases by another research controlvalve. The gas mixtures exiting reactor was analyzed by on-line GC andGC/MS connected through a hotbox valve arrangements to preventcondensation. The conversion of 1233xf was from about 50% to about 65%and the selectivity to 244 isomer (CF₃CFClCH₃) was from about 90% toabout 93% depending on the reaction conditions using 120 cc of 50 wt %SbCl₅/C as the catalyst at about 65° C. to about −85° C. with a HF flowof about 50 g/h and organic flow of about 15 g/h. No CF₃CF₂CH₃ wasobserved under the reaction conditions. The catalyst is pretreated atfirst with 50 g/h HF at about 65° C. for about 2 hours and then withabout 50 g/h HF and about 200 sccm of Cl₂ at about 65° C. for about 4hours. After pre-treatment, about 50 sccm of N2 is flows over a periodof about 40 minutes through the catalyst bed to sweep free chlorine fromthe catalyst surface prior to interacting with the organic feed(1233xf). Pretreatment is considered important to many embodiments ofthe invention. The products were collected by flowing the reactor exitgases through a 20-60 wt % aqueous KOH scrubber solution and thentrapping the exit gases from the scrubber into a cylinder kept in dryice or liquid N₂. The products were then isolated by distillation. About50 wt % SbCl₅/C, about 3 to about 6 wt % FeCl₃/C, 20 wt % SnCl₄/C, andabout 23 wt % TiCl₄/C, using 4 different kind of activated carbon suchas Shiro saga, Calgon, Norit, and Aldrich were used as the catalyst atfrom about 60 to about 150° C. Among all the catalysts used for thisreaction, Cl₂ and HF pre-treated SbCl₅/C was found to be generallypreferred in terms of activity. The results using SbCl₅ as the catalystare shown in Table 2.

TABLE 2 Catalyzed-gas-phase transformation of CF₃CCl═CH₂ to CF₃CFClCH₃Conv. of T CF₃CCl═CH₂ Selectivity for # Catalyst (° C.) (1233xf)CF₃CFClCH₃ 1 10 wt % SbCl₅/C 60 15 100 2 20 wt % SbCl₅/C 60 21 98 3 30wt % SbCl₅/C 60 32 98 4 50 wt % SbCl₅/C 60 55 97 5 50 wt % SbCl₅/C 80 6293 6 50 wt % SbCl₅/C 100 56 87 7 60 wt % SbCl₅/C 60 59 91 8 50 wt % 6034 92 SbCl₅/NORIT RFC3 Activated Carbon 9 50 wt % 60 56 96 SbCl₅/ShiroSaga Activated Carbon 10 50 wt % 60 57 94 SbCl₅/Aldrich Activated CarbonReaction conditions: 1233xf flow, 150 sccm; HF flow 50 g/h; pressure,2.5-5.3 psig; in 1-5 reactions Calgon activated carbon is used as thecatalyst support; catalyst, 120 cc. All catalysts are pre-treated withCl₂ and HF prior to contacting with 1233xf.

It should be understood that the foregoing description is onlyillustrative of the present invention. Various alternatives andmodifications can be devised by those skilled in the art withoutdeparting from the invention. Accordingly, the present invention isintended to embrace all such alternatives, modifications and variancesthat fall within the scope of the appended claims.

What is claimed is:
 1. A process for making2-chloro-1,1,1,2-tetrafluoropropane, comprising hydrofluorinating2-chloro-3,3,3-trifluoropropene in the presence of a catalyst selectedfrom the group consisting of SbCl₃, SbCl₅, SbF₅, TiCl₄, SnCl₄, Cr₂O₃,and fluorinated Cr₂O₃.
 2. The process of claim 1, wherein the catalystis in bulk form.
 3. The process of claim 1, wherein the catalyst issupported.
 4. The process of claim 3, wherein the support is selectedfrom the group consisting of carbon, alumina, fluorinated alumina, oraluminum fluoride.
 5. The process of claim 1 where the catalyst isactivated using anhydrous hydrogen fluoride.
 6. The process of claim 1where the catalyst is activated using anhydrous chlorine.
 7. The processof claim 1, wherein the hydrofluorination is vapor-phase fluorination.8. The process of claim 7, wherein the catalyst for vapor-phasefluorination reaction is SbCl₅ supported on activated carbon.
 9. Theprocess of claim 7, wherein the catalyst for vapor-phase fluorinationreaction is Cr₂O₃ bulk or supported.
 10. The process of claim 7, whereinthe catalyst for vapor-phase fluorination reaction is fluorinated Cr₂O₃bulk or supported.
 11. The process of claim 7, wherein the vapor-phasefluorination reaction is carried out at a temperature of about 50° C. toabout 120° C. and at a pressure of about 30 psia to about 175 psia. 12.The process of claim 7, wherein the mole ratio of hydrogen fluoride to2-chloro-3,3,3-trifluoropropene is from about 2:1 to about 15:1.
 13. Theprocess of claim 1, wherein the hydrofluorination is liquid-phasefluorination.
 14. The process of claim 13, wherein the catalyst forliquid-phase fluorination reaction is SbCl₅.
 15. The process of claim13, wherein the liquid-phase fluorination reaction is carried out at atemperature of about 50° C. to about 120° C. and at a pressure of about50 psia to about 175 psia.
 16. The process of claim 13, wherein the moleratio of hydrogen fluoride to 2-chloro-3,3,3-trifluoropropene is fromabout 2:1 to about 15:1.